Selenium-based monomers and conjugated polymers, methods of making, and use thereof

ABSTRACT

Substituted selenophene monomers, and polymers and copolymers having units derived from a substituted selenophene are disclosed. Also provided are methods of making and using the same.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. Nonprovisional patentapplication Ser. No. 13/406,925, filed Feb. 28, 2012, which claims thebenefit of U.S. Provisional Application Ser. No. 61/448,290, filed Mar.2, 2011. These priority applications are fully incorporated herein byreference.

TECHNICAL FIELD

This invention relates to selenium-based monomers, selenium-basedconjugated polymers prepared therefrom, methods of producing themonomers and conjugated polymers, and applications utilizing theconjugated polymers.

BACKGROUND

Poly-3,4-ethylenedioxythiophene (“PEDOT”) prepared from3,4-ethylenedioxythiophene (“EDOT”) is a well known conducting polymer.Higher photopic contrast and a more colorless bleached state is obtainedby incorporation of an additional methylene unit into the EDOT repeatunit with 3,4-propylenedioxythiophene (“PropOT”). PolyPropOT exhibitsenhanced electrochromic properties over conducting polymer PEDOT.PPropOT has a Δ% T of 66% at 2 mlax compared to the 54% transmittancechange for PEDOT (Sommen, G. L. Mini-Rev. Org. Chem. 2005, 2, 375).

Theoretical studies and calculations indicate that selenophene basedpolymers should have a lower band gap (E_(g)) than correspondingpolythiophenes. Due to the larger size of selenium, polyselenophenes arealso expected to have some advantages over polythiophenes, such ashaving lower oxidation and reduction potentials, being easier topolarize, and being more suitable for interchain charge transfer (whichis facilitated by the intermolecular contacts between Se atoms).

Poly(3,4-ethylenedioxyselenophene) (“PEDOS”) has been synthesized(Patra, A.; Wijsboom, Y. H.; Zade, S. S.; Li, M.; Sheynin, Y.; Leitus,G.; Bendikov, M. J. Am. Chem. Soc. 2008. 130, 6735) and is reported toexhibit a band gap of 1.4 eV. The polymer PEDOS is highly stable in itsoxidized state and has well defined spectroelectrochemistry. It also hasa lower band gap than PEDOT (1.6-1.7 eV).

Selenium based conductive polymers offer several challenges. Dopedpolyselenophenes show significantly lower conductivities (10⁻⁴ to 10⁻¹S/cm) than that of doped polythiophenes (up to 10³ S/cm). The lack of awell-defined electrochemical response prevents their study andapplication and there are synthetic challenges for the synthesis ofsubstituted selenophene-based monomeric precursors. It is presumed thatthe low conductivity and poor electrochemical behavior ofpolyselenophenes results from their instability during oxidativepolymerization.

Accordingly, there remains a need in the art for new, substitutedpolyselenophenes with high conductivity and well-definedelectrochemistry.

BRIEF SUMMARY OF THE INVENTION

In one embodiment, a polymer comprises a unit derived from a monomeraccording to structure (I):

wherein each instance of Q is O or S;

each of R^(1a), R^(1b), R^(2a), R^(2b), R³, and R⁴ independently ishydrogen; C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl, C₁-C₂₀ alkoxy, C₁-C₂₀haloalkoxy, aryloxy, —C₁-C₁₀ alkyl-O—C₁-C₁₀ alkyl, —C₁-C₁₀ alkyl-O-aryl,—C₁-C₁₀ alkyl-aryl; or hydroxyl;

with the proviso that at least one of R^(1a), R^(1b), R^(2a), R^(2b),R³, and R⁴ is not hydrogen, and when R^(1a), R^(1b), R^(2a), and R^(2b)are all hydrogen, then at least one of R³ and R⁴ is other than hydrogen,methyl, or ethyl;

wherein the C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl, C₁-C₂₀ alkoxy, C₁-C₂₀haloalkoxy, aryloxy, —C₁-C₁₀ alkyl-O—C₁-C₁₀ alkyl, —C₁-C₁₀ alkyl-O-aryl,—C₁-C₁₀ alkyl-aryl group each may be optionally substituted with one ormore of C₁-C₂₀ alkyl; aryl; halogen; hydroxyl; —N—(R⁷)₂ wherein each R⁷is independently hydrogen or C₁-C₆ alkyl; cyano; nitro; —COOH;—S(═O)C₀-C₁₀ alkyl; or —S(═O)₂C₀-C₁₀ alkyl.

In another embodiment, a method comprises polymerizing a composition byelectrochemical or chemical reaction to form a polymer, wherein thecomposition comprises a monomer according to the structure (I) or (Ia):

wherein each instance of Q is O or S;

each of R^(1a), R^(1b), R^(2a), R^(2b), R³, and R⁴ independently ishydrogen; C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl, C₁-C₂₀ alkoxy, C₁-C₂₀haloalkoxy, aryloxy, —C₁-C₁₀ alkyl-O—C₁-C₁₀ alkyl, —C₁-C₁₀ alkyl-O-aryl,—C₁-C₁₀ alkyl-aryl; or hydroxyl;

with the proviso that at least one of R^(1a), R^(1b), R^(2a) R^(2b), R³,and R⁴ is not hydrogen, and when R^(1a), R^(1b), R^(2a), and R^(2b) areall hydrogen, then at least one of R³ and R⁴ is other than hydrogen,methyl, or ethyl;

wherein the C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl, C₁-C₂₀ alkoxy, C₁-C₂₀haloalkoxy, aryloxy, —C₁-C₁₀ alkyl-O—C₁-C₁₀ alkyl, —C₁-C₁₀ alkyl-O-aryl,—C₁-C₁₀ alkyl-aryl group each may be optionally substituted with one ormore of C₁-C₂₀ alkyl; aryl; halogen; hydroxyl; —N—(R⁷)₂ wherein each R⁷is independently hydrogen or C₁-C₆ alkyl; cyano; nitro; —COOH;—S(═O)C₀-C₁₀ alkyl; or —S(═O)₂C₀-C₁₀ alkyl; and

X is chloro, bromo, or iodo.

In yet another embodiment, a compound comprises a monomer according toany one of structure (I), (Ia), (II), and (IIa):

wherein each instance of Q is O or S;

X is chloro, bromo, or iodo;

each of R^(1a), R^(1b), R^(2b), R³, and R⁴ independently is hydrogen;C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl, C₁-C₂₀ alkoxy, C₁-C₂₀ haloalkoxy,aryloxy, —C₁-C₁₀ alkyl-O—C₁-C₁₀ alkyl, —C₁-C₁₀ alkyl-O-aryl, —C₁-C₁₀alkyl-aryl; or hydroxyl;

with the proviso that at least one of R^(1a), R^(1b), R^(2a) R^(2b), R³,and R⁴ is not hydrogen, and when R^(1a), R^(1b), R^(2a), and R^(2b) areall hydrogen, then at least one of R³ and R⁴ is other than hydrogen,methyl, or ethyl;

wherein the C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl, C₁-C₂₀ alkoxy, C₁-C₂₀haloalkoxy, aryloxy, —C₁-C₁₀ alkyl-O—C₁-C₁₀ alkyl, —C₁-C₁₀ alkyl-O-aryl,—C₁-C₁₀ alkyl-aryl group each may be optionally substituted with one ormore of C₁-C₂₀ alkyl; aryl; halogen; hydroxyl; —N—(R⁷)₂ wherein each R⁷is independently hydrogen or C₁-C₆ alkyl; cyano; nitro; —COOH;—S(═O)C₀-C₁₀ alkyl; or —S(═O)₂C₀-C₁₀ alkyl.

In still yet another embodiment, a method of preparing a compoundaccording to the structure (I):

wherein each instance of Q is O;

each of R^(1a), R^(1b), R^(2a), R^(2b), R³, and R⁴ independently ishydrogen; C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl, C₁-C₂₀ alkoxy, C₁-C₂₀haloalkoxy, aryloxy, —C₁-C₁₀alkyl-O—C₁-C₁₀ alkyl, —C₁-C₁₀ alkyl-O-aryl,—C₁-C₁₀ alkyl-aryl; or hydroxyl;

with the proviso that at least one of R^(1a), R^(1b), R^(2a), and R^(2b)is not hydrogen;

wherein the C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl, C₁-C₂₀ alkoxy, C₁-C₂₀haloalkoxy, aryloxy, —C₁-C₁₀alkyl-O—C₁-C₁₀ alkyl, —C₁-C₁₀alkyl-O-aryl,—C₁-C₁₀alkyl-aryl group each may be optionally substituted with one ormore of C₁-C₂₀ alkyl; aryl; halogen; hydroxyl; —N—(R⁷)₂ wherein each R⁷is independently hydrogen or C₁-C₆ alkyl; cyano; nitro; —COOH;—S(═O)C₀-C₁₀ alkyl; or —S(═O)₂C₀-C₁₀ alkyl, comprises reacting a3,4-dialkoxyselenophene with a substituted diol.

Other embodiments include articles and devices prepared from thepolymers disclosed herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the in-situ spectroelectrochemistry of PProDOS-Me₂deposited onto ITO-coated-glass in 0.1 M TBAPF₆/ACN.

FIG. 2 is illustrates the in-situ spectroelectrochemistry ofPProDOS-Hexyl₂ deposited onto ITO-coated-glass in 0.1 M TBAPF₆/ACN.

DETAILED DESCRIPTION OF THE INVENTION

Disclosed herein are substituted 3,4-propylenedioxyselenophene monomers(“substituted ProDOS monomers”) substituted at the 1, 3 or 1 and 3positions of the propylene moiety (i.e. alpha to the monomer oxygen(s)),and optionally further substituted at the 2 position, the centralmethylene unit. Also disclosed are the corresponding substituted3,4-propylenedithioselenophene monomers (“substituted PropTS monomers”),substituted at the 1, 3 or 1 and 3 positions of the propylene moiety,and optionally further substituted at the 2 position. The substitutedProDOS monomers and substituted PropTS monomers are collectivelyreferred to as ProDOS/DTS monomers. Upon conjugation, the resultingelectrochromic conjugated polymers (“substituted ProDOS polymers”,“substituted PropTS polymers” and “substituted ProDOS/DTS polymer”)exhibit different colors in the reduced state that are blue shifted fromconventional polypropylenedioxyselenophene, which is a deep blue.

The high optical transparency in the oxidized state is controlled by theconductivity of the polymer. Introduction of disorder into the structureis one method for decreasing interchain carrier mobility resulting in adecrease in the intensity of the optical transition occurring at the lowenergy of the near infrared region (NIR), one factor in obtaining acolorless oxidized state. By adding substitution at the 1, 3, or 1 and 3positions of the 3,4-propylenedioxyselenophene and3,4-propylenethioselenophene core will provide a disruption ofconjugation of the polymer in order to increase the energy of the pi-pi*transition. The substitution will introduce steric interactions thatwould decrease interchain interactions of the polymer thereby increasingthe optical transparency in the bleached state. Not wishing to be boundby theory, it is theorized the alpha substituents would project over theconjugated polymer backbone thereby causing steric interactions todistort selenophenes of the backbone out of planarity compared tounsubstituted 3,4-propylenedioxyselenopene/3,4-propylenethioselenophenepolymers or even the 3,4-propylenedioxyselenopene polymers where thecentral carbon of ProDOS is substituted with alkyl groups. Thedistortion of planarity is expected to be proportional to the size ofthe substituent groups. Ditertbutyl substituents are expected to furtherblue shift the λmax with respect to the dimethyl substituents. As thesubstituent increases in size (e.g. increasing size of alkyl groups) itis anticipated that the polymer should transition to a highlytransparent state in the semiconductive form. Longer alkyl substituentswould further provide solubilization in organic solvents for improvedsolution processability.

Polymerized substituted ProDOS/DTS are excellent electrochromicmaterials in terms of their contrast ratios and Coloration Efficiency,while retaining stability and switching time characteristics comparableto those of PEDOT derivatives. The polymerized substituted ProDOS/DTSexhibit higher charge carrier mobilities compared to the analogousall-thiophene systems. The increased atomic radius of selenium (103 pm(picometer)) over sulfur (88 pm) enhances molecular overlaps betweenpolymer chains, and facilitates the charge hopping process. The use ofselenium results in a red-shift of the maximum absorbance wavelengthover the all-thiophene systems (e.g. PEDOT). With proper substitution atthe 1 and 3 positions of the substituted ProDOS/DTS, it is possible tomake full color spectrum from a single molecular approach.

The polymerized substituted ProDOS/DTS will exhibit advantages overknown conjugated polymers used for light display applications as lightdisplays prepared thereform can easily be tuned in terms of color andcolor intensity. The substituted selenophene will have a lower oxidationpotential and higher electron donating character than the sulfuranalogue which helps the device to work at a lower potential window.Lower oxidation potential engenders high quality polymer films duringelectropolymerization by negating the harmful effects of highpolymerization potentials which causes the degradation of the polymerfilms. Selenium is easier to polarize than sulfur, and is more suited tointerchain charge transfer which should be facilitated by intermolecularSe . . . Se contacts.

The substituted ProDOS/DTS polymer exhibits low band gaps, can be p- andn-dopable as the selenium atom is more easily polarized than sulfur, thepolymer is prepared from an electron rich monomer, and the substitutedProDOS/DTS polymer can be made processable from common organic solventsby proper choice of substituents.

The starting substituted ProDOS/DTS monomers used to prepare thesubstituted ProDOS/DTS polymers include those according to the generalstructure (I):

wherein each instance of Q is O or S; each of R^(1a), R^(1b), R^(2a),R^(2b), R³, and R⁴ independently is hydrogen; optionally substitutedC₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl, C₁-C₂₀ alkoxy, C₁-C₂₀ haloalkoxy,aryloxy, —C₁-C₁₀ alkyl-O—C₁-C₁₀ alkyl, —C₁-C₁₀ alkyl-O-aryl, —C₁-C₁₀alkyl-aryl; or hydroxyl; with the proviso that at least one of R^(1a),R^(1b), R^(2a), R^(2b), R³, and R⁴ is not hydrogen, and when R^(1a),R^(1b), R^(2a), and R^(2b) are all hydrogen, then at least one of R³ andR⁴ is other than hydrogen, methyl, or ethyl. The C₁-C₂₀ alkyl, C₁-C₂₀haloalkyl, aryl, C₁-C₂₀ alkoxy, C₁-C₂₀ haloalkoxy, aryloxy, —C₁-C₁₀alkyl-O—C₁-C₁₀ alkyl, —C₁-C₁₀ alkyl-O-aryl, or —C₁-C₁₀ alkyl-aryl groupseach may be optionally substituted with one or more of C₁-C₂₀ alkyl;aryl; halogen; hydroxyl; —N—(R⁷)₂ wherein each R⁷ is independentlyhydrogen or C₁-C₆ alkyl; cyano; nitro; —COOH; —S(═O)C₀-C₁₀ alkyl; or—S(═O)₂C₀-C₁₀ alkyl.

In one embodiment, each of R^(1a), R^(1b), R^(2a) and R^(2b)independently is R^(1b) hydrogen; optionally substituted C₁-C₁₀ alkyl,C₁-C₁₀haloalkyl, aryl, C₁-C₁₀ alkoxy, C₁-C₁₀ haloalkoxy, aryloxy, —C₁-C₅alkyl-O—C₁-C₅ alkyl, —C₁-C₅ alkyl-O-aryl, —C₁-C₅ alkyl-aryl; orhydroxyl; and R³ and R⁴ are both hydrogen; with the proviso that atleast one of R^(1a), R^(1b), R^(2a) and R^(2b) is not hydrogen. TheC₁-C₁₀ alkyl, C₁-C₁₀ haloalkyl, aryl, C₁-C₁₀ alkoxy, C₁-C₁₀ haloalkoxy,aryloxy, —C₁-C₅ alkyl-O—C₁-C₅ alkyl, —C₁-C₅ alkyl-O-aryl, or —C₁-C₅alkyl-aryl groups each may be optionally substituted with one or more ofC₁-C₂₀ alkyl; aryl; halogen; hydroxyl; —N—(R⁷)₂ wherein each R⁷ isindependently hydrogen or C₁-C₆ alkyl; cyano; nitro; —COOH; —S(═O)C₀-C₁₀alkyl; or —S(═O)₂C₀-C₁₀ alkyl.

In another embodiment, each of R^(1a), R^(1b), R^(2a) and R^(2b)independently is hydrogen; optionally substituted C₁-C₅ alkyl, C₁-C₅haloalkyl, aryl, C₁-C₅ alkoxy, C₁-C₅ haloalkoxy, aryloxy, —C₁-C₃alkyl-O—C₁-C₃ alkyl, —C₁-C₃ alkyl-O-aryl, —C₁-C₃ alkyl-aryl; orhydroxyl; and R³ and R⁴ are both hydrogen; with the proviso that atleast one of R^(1a), R^(1b), R^(2a) and R^(2b) is not hydrogen. TheC₁-C₅ alkyl, C₁-C₅ haloalkyl, aryl, C₁-C₅ alkoxy, C₁-C₅ haloalkoxy,aryloxy, —C₁-C₃ alkyl-O—C₁-C₃ alkyl, —C₁-C₃ alkyl-O-aryl, or —C₁-C₃alkyl-aryl groups each may be optionally substituted with one or more ofC₁-C₂₀ alkyl; aryl; halogen; hydroxyl; —N—(R⁷)₂ wherein each R⁷ isindependently hydrogen or C₁-C₆ alkyl; cyano; nitro; —COOH; —S(═O)C₀-C₁₀alkyl; or —S(═O)₂C₀-C₁₀ alkyl.

In one embodiment, both Q groups are O. In another embodiment, both Qgroups are S.

In one embodiment, at least two of R^(1a), R^(1b), R^(2a), and R^(2b)are not hydrogen while the remaining two groups are hydrogen. In anadditional embodiment, both R^(1a) and R^(1b) or both R^(2a) and R^(2b)are hydrogen while the remaining two groups are other than hydrogen.

In one embodiment, each of R^(1a), R^(1b), R^(2a), and R^(2b)independently is hydrogen; or optionally substituted C₁-C₂₀ alkyl,C₁-C₂₀ haloalkyl, aryl, —C₁-C₁₀ alkyl-aryl; and R³ and R⁴ are bothhydrogen; with the proviso that at least one of R^(1a), R^(1b), R^(2a),and R^(2b) is not hydrogen. The C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl,—C₁-C₁₀ alkyl-aryl groups each may be optionally substituted with one ormore of C₁-C₂₀ alkyl; aryl; halogen; hydroxyl; —N—(R⁷)₂ wherein each R⁷is independently hydrogen or C₁-C₆ alkyl; cyano; nitro; —COOH;—S(═O)C₀-C₁₀ alkyl; or —S(═O)₂C₀-C₁₀ alkyl.

In another embodiment, each of R^(1a), R^(1b), R^(2a), and R^(2b)independently is hydrogen; or optionally substituted C₁-C₂₀ alkyl,C₁-C₂₀ haloalkyl, aryl, —C₁-C₁₀ alkyl-aryl; and R³ and R⁴ are bothhydrogen; with the proviso that at least two of R^(1a), R^(1b), R^(2a),and R^(2b) are not hydrogen. The C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl,—C₁-C₁₀ alkyl-aryl groups each may be optionally substituted with one ormore of C₁-C₂₀ alkyl; aryl; halogen; hydroxyl; —N—(R⁷)₂ wherein each R⁷is independently hydrogen or C₁-C₆ alkyl; cyano; nitro; —COOH;—S(═O)C₀-C₁₀ alkyl; or —S(═O)₂C₀-C₁₀ alkyl.

In yet another embodiment, R^(1a), R^(1b), R^(2a), and R^(2b) are allhydrogen; R³, and R⁴ are each independently optionally substitutedC₃-C₂₀ alkyl, C₃-C₂₀ haloalkyl, aryl, C₃-C₂₀ alkoxy, C₃-C₂₀ haloalkoxy,aryloxy, —C₁-C₁₀ alkyl-O—C₁-C₁₀ alkyl, —C₁-C₁₀ alkyl-O-aryl, —C₃-C₁₀alkyl-aryl; specifically substituted C₄-C₁₀ alkyl, C₄-C₁₀ haloalkyl,aryl, C₄-C₁₀ alkoxy, C₄-C₁₀ haloalkoxy, aryloxy, —C₁-C₅ alkyl-O—C₁-C₅alkyl, —C₁-C₅ alkyl-O-aryl, —C₄-C₈ alkyl-aryl. In one embodiment,R^(1a), R^(1b), R^(2a), and R^(2b) are all hydrogen; R³ and R⁴ are both—(CH₂)₃CH₃; —(CH₂)₇CH₃; or —CH₂OC(O)(CH₂)₅CH₃.

The starting substituted ProDOS/DTS monomers to prepare the substitutedProDOS polymers include those according to the general structure (II):

wherein Q, R^(1a), R^(1b), R^(2a), and R^(2b) are as described above.

In one embodiment, the substituted ProDOS/DTS monomer meets the generalstructure (II) wherein each of R^(1a) and R^(1b) independently is C₁-C₁₀alkyl or benzyl and each of R^(2a) and R^(2b) independently is hydrogen,C₁-C₁₀ alkyl, or benzyl. In another embodiment, the substitutedProDOS/DTS monomer meets the general structure (II) wherein each ofR^(1a) and R^(1b) independently is C₁-C₅ alkyl or benzyl and each ofR^(2a) and R^(2b) independently is hydrogen, C₁-C₅ alkyl, or benzyl. Instill yet another embodiment, the substituted ProDOS monomer meets thegeneral structure (II) wherein each of R^(1a) and R^(1b) independentlyis C₁-C₃ alkyl or benzyl and each of R^(2a) and R^(2b) independently ishydrogen, C₁-C₃ alkyl, or benzyl. In yet another embodiment, thesubstituted ProDOS monomer meets the general structure (II) wherein eachof R^(1a) and R^(1b) independently is methyl, isopropyl, tert-butyl,n-hexyl, or benzyl and each of R^(2a) and R^(2b) independently ishydrogen.

In other embodiments, the substituted ProDOS/DTS monomers include thoseaccording to the general structures (Ia) and (IIa)

wherein Q, R^(1a), R^(1b), R^(2a), and R^(2b) are as described above andX is Cl, Br, or I.

The substituted ProDOS/DTS monomers can be prepared from a convenientsynthetic path. In one embodiment, the substituted ProDOS monomers canbe prepared via a trans-etherification reaction of3,4-dialkoxyselenophene with an appropriately substituted diol accordingto the general Scheme A below.

The starting 3,4-dialkoxyselenophene can have a lower alkyl substituentfor R⁵, specifically a C₁-C₄ alkyl, and more specifically a C₁-C₂ alkyl.

The substituted diol according to general Scheme A contains groupsR^(1a), R^(1b), R^(2a), R^(2b), R³, and R⁴ as defined above, or theirappropriately protected functional group equivalents. Commerciallyavailable diols include 2,4-pentanediol, 2-methyl-2,4-pentanediol,2,4-dimethyl-2,4-pentanediol, 3-methyl-2,4-heptanediol, and7-ethyl-2-methyl-4,6-nonanediol, all of which are available fromSigma-Aldrich

The reaction of the 3,4-dialkoxyselenophene and diol is performed in thepresence of a catalyst. Exemplary catalysts include sulfonic acids suchas p-toluene sulfonic acid, dodecylbenzene sulfonic acid, and the like.

The solvent used in the reaction to prepare the substituted ProDOSmonomer can be any high boiling, inert organic solvent including anaromatic such as toluene, xylene, and the like; and a halogenatedaromatic including ortho-dichlorobenzene; mixtures thereof; and thelike.

The temperature of the reaction to prepare the substituted ProDOSmonomer can be at or about the boiling point of the solvent used.Specifically the reaction can be performed at temperatures of about 80to about 300° C., more specifically about 90 to about 250° C., yet morespecifically about 100 to about 200° C.

Substituted PropTS can be synthesized in an analogous fashion to ProDOSdescribed above except that a dithiol is used. An exemplary dithiol isaccording to the structure

where R^(1a), R^(1b), R^(2a), R^(2b), R³, and R⁴ are as previouslydefined.

Exemplary ProDOS/DTS monomers include those provided in the followingtable.

(I)

Structure (I) Q R^(1a) R^(2a) R^(1b) R^(2b) R³ R⁴ O —CH₃ H —CH₃ H H H O—CH₃ —CH₃ —CH₃ —CH₃ H H O —CH₂CH₃ H —CH₂CH₃ H H H O —(CH₂)₂CH₃ H—(CH₂)₂CH₃ H H H O —CH(CH₃)₂ H —CH(CH₃)₂ H H H O —(CH₂)₃CH₃ H —(CH₂)₃CH₃H H H O —CH₂CH(CH₃)₂ H —CH₂CH(CH₃)₂ H H H O —C(CH₃)₃ H —C(CH₃)₃ H H H O—C₆H₁₃ H —C₆H₁₃ H H H O —C₈H₁₇ H —C₈H₁₇ H H H O CH(C₂H₅)(C₆H₁₃) HCH(C₂H₅)(C₆H₁₃) H H H O —C₁₂H₂₅ H —C₁₂H₂₅ H H H O —C₁₈H₃₇ H —C₁₈H₃₇ H HH O —C₅H₉ H —C₅H₉ H H H O —CH₂Ph H —CH₂Ph H H H O —CH₂Ph —CH₂Ph —CH₂Ph—CH₂Ph H H S —CH₃ H —CH₃ H H H S —CH₃ —CH₃ —CH₃ —CH₃ H H S —CH₂CH₃ H—CH₂CH₃ H H H S —(CH₂)₂CH₃ H —(CH₂)₂CH₃ H H H S —CH(CH₃)₂ H —CH(CH₃)₂ HH H S —(CH₂)₃CH₃ H —(CH₂)₃CH₃ H H H S —CH₂CH(CH₃)₂ H —CH₂CH(CH₃)₂ H H HS —C(CH₃)₃ H —C(CH₃)₃ H H H S —C₆H₁₃ H —C₆H₁₃ H H H S —C₈H₁₇(CH₂)₇CH₃ H—C₈H₁₇(CH₂)₇CH₃ H H H S —CH₂Ph H —CH₂Ph H H H S —CH₂Ph —CH₂Ph —CH₂Ph—CH₂Ph H H S CH(C₂H₅)(C₆H₁₃) H CH(C₂H₅)(C₆H₁₃) H H H S —C₁₂H₂₅ H —C₁₂H₂₅H H H S —C₁₈H₃₇ H —C₁₈H₃₇ H H H S —C₅H₉ H —C₅H₉ H H H O H H H H—(CH₂)₃CH₃ —(CH₂)₃CH₃ O H H H H —(CH₂)₇CH₃ —(CH₂)₇CH₃ O H H H H—CH₂OC(O)(CH₂)₅CH₃ —CH₂OC(O)(CH₂)₅CH₃ O H H H H —CH₂O(2-EthylHexyl)—CH₂O(2-EthylHexyl) O H H H H CH₂Ph CH₂Ph S H H H H —(CH₂)₃CH₃—(CH₂)₃CH₃ S H H H H —(CH₂)₇CH₃ —(CH₂)₇CH₃ S H H H H —CH₂OC(O)(CH₂)₅CH₃—CH₂OC(O)(CH₂)₅CH₃ S H H H H —CH₂O(2-EthylHexyl) —CH₂O(2-EthylHexyl) S HH H H CH₂Ph CH₂Ph

Also disclosed herein are conductive conjugated polymers that areobtained via conversion of a substituted ProDOS/DTS monomer via chemicaloxidation or electrochemical oxidation. These substituted ProDOS/DTSpolymers have utilities in a wide variety of applications, for example,electronic packaging, organic light-emitting diodes (LEDs),electrochromic windows and displays, optically transparent electrodes,volatile organic gas sensors, as well as other applications discussedherein.

The substituted ProDOS/DTS monomers disclosed herein can be polymerizedalone to form a conjugated homopolymer.

Also provided herein are copolymers comprising units derived from two ormore different substituted ProDOS/DTS monomers. Also provided herein arecopolymers comprising units derived from a substituted ProDOS/DTS and anadditional monomer (“co-monomer”) which provide a tailoring of theconductivity or optoelectronic properties of the resulting polymer. Theco-monomer can include electroactive monomers or non-electroactivemonomers. “Electroactive monomer” as used herein means a monomer oroligomer that is capable of copolymerization with substitutedProDOS/DTS, and that imparts or enhances the electrical/electronicproperties of the resulting copolymer, including such properties aselectrical conductivity, semiconductivity, electroluminescence,electrochromicity, photovoltaic properties, or the like.“Non-electroactive monomer” means a monomer that is capable ofcopolymerization and that either decreases or does not adversely affectthe electrical/electronic properties of the resulting copolymer.

Examples of suitable electroactive monomers include those known in theart to exhibit electroactivity, including but not limited to thiophene,substituted thiophene, thieno[3,4-b]thiophene, substitutedthieno[3,4-b]thiophene, dithieno[3,4-b:3′,4′-d]thiophene,thieno[3,4-b]furan, substituted thieno[3,4-b]furan, bithiophene,substituted bithiophene, selenophene, substituted selenophene, pyrrole,substituted pyrrole, phenylene, substituted phenylene, naphthalene,substituted naphthalene, biphenyl and terphenyl and their substitutedversions, phenylene vinylene, substituted phenylene vinylene, and thelike.

Suitable co-monomers include unsubstituted and 2- or 6-substitutedthieno[3,4-b]thiophene and thieno[3,4-b]furan having the generalstructures (III), (IV), and (V):

wherein Q¹ is S or O; and R⁶ is hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkylincluding perfluoroalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl. Specifically, Q¹ is S or O;and R⁶ is hydrogen.

Derivatives having the general structures (VI), (VII), and (VII):

wherein G¹ is S or Se; G² is S, Se, or O wherein at least one of G¹ orG² is Se; and R⁶ is hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl includingperfluoroalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl. Specifically, G¹ is S orSe; G² is S or Se; and R⁶ is hydrogen.

3,4-Ethylenedioxythiophene, 3,4-ethylenedithiathiophene,3,4-ethylenedioxypyrrole, 3,4-ethylenedithiapyrrole,3,4-ethylenedioxyfuran, 3,4-ethylenedithiafuran, and derivatives havingthe general structure (IX):

wherein each occurrence of Q¹ is independently S or O; Q² is S, O, orN—R⁷ wherein R⁷ is hydrogen or C₁-C₆ alkyl; and each occurrence of R⁶ ishydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl.

Seleno derivatives having the general structure (X):

wherein each occurrence of Q¹ is independently S or O; and eachoccurrence of R⁶ is hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆alkyl-O-aryl.

Isathianaphthene, pyridothiophene, pyrizinothiophene, and derivativeshaving the general structure (XI):

wherein Q² is S, O, or N—R⁷ wherein R⁷ is hydrogen or C₁-C₆ alkyl; eachoccurrence of Q³ is independently CH or N; and each occurrence of R⁶ isindependently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy,C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆alkyl-O-aryl.

Oxazole, thiazole, and derivatives having the general structure (XII):

wherein Q¹ is S or O.

Pyrrole, furan, thiophene, and derivatives having the general structure(XIII):

wherein Q² is S, O, or N—R⁷ wherein R⁷ is hydrogen or C₁-C₆ alkyl; andeach occurrence of R⁶ is independently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆alkyl, or —C₁-C₆ alkyl-O-aryl.

Selenophene and derivatives having the general structure (XIV):

wherein each occurrence of R⁶ is independently hydrogen, C₁-C₁₂ alkyl,C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl.

Bithiophene, bifuran, bipyrrole, and derivatives having the followinggeneral structure (XV):

wherein each occurrence of Q² is independently S, O, or N—R⁷ wherein R⁷is hydrogen or C₁-C₆ alkyl; and each occurrence of R⁶ is independentlyhydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl.

Biselenophene and derivatives having the following general structure(XVI):

wherein each occurrence of R⁶ is independently hydrogen, C₁-C₁₂ alkyl,C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl.

Terthiophene, terfuran, terpyrrole, and derivatives having the followinggeneral structure (XVII):

wherein each occurrence of Q² is independently S, O, or N—R⁷ wherein R⁷is hydrogen or C₁-C₆ alkyl; and each occurrence of R⁶ is independentlyhydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl.

Terselenophene and derivatives having the following general structure(XVIII):

wherein each occurrence of R⁶ is independently hydrogen, C₁-C₁₂ alkyl,C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl.

Thienothiophene, thienofuran, thienopyrrole, furanylpyrrole,furanylfuran, pyrolylpyrrole, and derivatives having the followinggeneral structure (XIX):

wherein each occurrence of Q² is independently S, O, or N—R⁷ wherein R⁷is hydrogen or C₁-C₆ alkyl; and each occurrence of R⁶ is independentlyhydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl.

Dithienothiophene, difuranylthiophene, dipyrrolylthiophene,dithienofuran, dipyrrolylfuran, dipyrrolylpyrrole, and derivativeshaving the following general structure (XX):

wherein each occurrence of Q² is independently S, O, or N—R⁷ wherein R⁷is hydrogen or C₁-C₆ alkyl; Q⁴ is C(R⁶)₂, S, O, or N—R⁷; and eachoccurrence of R⁶ is independently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆alkyl, or —C₁-C₆ alkyl-O-aryl.

Dithienylcyclopentenone, difuranylcyclopentenone,dipyrrolylcyclopentenone and derivatives having the following generalstructure (XXI):

wherein each occurrence of Q² is independently S, O, or N—R⁷ wherein R⁷is hydrogen or C₁-C₆ alkyl; and E is O or C(R⁸)₂, wherein eachoccurrence of R⁸ is an electron withdrawing group.

Other suitable heteroaryl monomers include those having the followinggeneral structure (XXII):

wherein each occurrence of Q¹ is independently S or O; each occurrenceof Q² is independently S, O, or N—R⁷ wherein R⁷ is hydrogen or C₁-C₆alkyl; each occurrence of R⁶ is independently hydrogen, C₁-C₁₂ alkyl,C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl. In one embodiment, eachoccurrence of Q¹ is O; each occurrence of Q² is S; and each occurrenceof R⁶ is hydrogen.

Seleno derivatives having the following general structure (XXIII):

wherein each occurrence of Q¹ is independently S or O; each occurrenceof R⁶ is independently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆alkyl-O-aryl. In one embodiment, each occurrence of Q¹ is O and eachoccurrence of R⁶ is hydrogen.

Dithienovinylene, difuranylvinylene, and dipyrrolylvinylene according tothe structure (XXIV):

wherein each occurrence of Q² is independently S, O, or N—R⁷ wherein R⁷is hydrogen or C₁-C₆ alkyl; each occurrence of R⁶ is independentlyhydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl;and each occurrence of R⁹ is hydrogen, C₁-C₆ alkyl, or cyano.

1,2-Trans(3,4-ethylenedioxythienyl)vinylene,1,2-trans(3,4-ethylenedioxyfuranyl)vinylene,1,2-trans(3,4-ethylenedioxypyrrolyl)vinylene, and derivatives accordingto the structure (XXV):

wherein each occurrence of Q³ is independently CH₂, S, or O; eachoccurrence of Q² is independently S, O, or N—R⁷ wherein R⁷ is hydrogenor C₁-C₆ alkyl; each occurrence of R⁶ is independently hydrogen, C₁-C₁₂alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl; and each occurrence of R⁹is hydrogen, C₁-C₆ alkyl, or cyano.

The class bis-thienylarylenes, bis-furanylarylenes, bis-pyrrolylarylenesand derivatives according to the structure (XXVI):

wherein each occurrence of Q² is independently S, O, or N—R⁷ wherein R⁷is hydrogen or C₁-C₆ alkyl; each occurrence of R⁶ is independentlyhydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl;and

represents an aryl. Exemplary aryl groups include furan, pyrrole,N-substituted pyrrole, phenyl, biphenyl, thiophene, fluorene,9-alkyl-9H-carbazole, and the like.

The class of bis(3,4-ethylenedioxythienyl)arylenes, related compounds,and derivatives according to the structure (XXVII):

wherein each occurrence of Q¹ is independently S or O; each occurrenceof Q² is independently S, O, or N—R⁷ wherein R⁷ is hydrogen or C₁-C₆alkyl; each occurrence of R⁶ is independently hydrogen, C₁-C₁₂ alkyl,C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl; and

represents an aryl.

An exemplary bis(3,4-ethylenedioxythienyl)arylenes according tostructure (XXVII) includes the compound wherein all Q¹ are O, both Q²are S, all R⁶ are hydrogen, and

is phenyl linked at the 1 and 4 positions. Another exemplary compound iswhere all Q¹ are O, both Q² are S, all R⁶ are hydrogen, and

is thiophene linked at the 2 and 5 positions.

The class of compounds according to structure (XXVIII):

wherein each occurrence of Q¹ is independently S or O; each occurrenceof Q² is independently S, O, or N—R⁷ wherein R⁷ is hydrogen or C₁-C₆alkyl; Q⁴ is C(R⁶)₂, S, O, or N—R⁷; and each occurrence of R⁶ isindependently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy,C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, or —C₁-C₆alkyl-O-aryl. In one embodiment, each occurrence of Q¹ is O; eachoccurrence of Q² is S; each occurrence of R⁶ is hydrogen; and R⁷ ismethyl.

The class of compounds according to structure (XXIX):

wherein each occurrence of Q² is independently S, O, or N—R⁷ wherein R⁷is hydrogen or C₁-C₆ alkyl; Q⁴ is C(R⁶)₂, S, O, or N—R⁷; and eachoccurrence of R⁶ is independently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆alkyl, or —C₁-C₆ alkyl-O-aryl.

The class of compounds according to structure (XXX):

wherein each occurrence of Q² is independently S, O, or N—R⁷ wherein R⁷is hydrogen or C₁-C₆ alkyl; each occurrence of Q⁴ is C(R⁶)₂, S, O, orN—R⁷; and each occurrence of R⁶ is independently hydrogen, C₁-C₁₂ alkyl,C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl.

The class of compounds according to structure (XXXI):

wherein Q² is S, O, or N—R⁷ wherein R⁷ is hydrogen or C₁-C₆ alkyl; andeach occurrence of Q¹ is independently S or O.

The class of compounds according to structure (XXXII):

wherein each occurrence of Q² is independently S, O, or N—R⁷ wherein R⁷is hydrogen or C₁-C₆ alkyl; and each occurrence of Q¹ is independently Sor O.

The class of compounds according to structure (XXXIII):

wherein Q² is S, O, or N—R⁷ wherein R⁷ is hydrogen or C₁-C₆ alkyl; eachoccurrence of Q¹ is independently S or O; and each occurrence of R⁶ isindependently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy,C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆ alkyl, —C₁-C₆ alkyl-aryl,—C₁-C₆ alkyl-O-aryl, or —C₁-C₆ alkyl-O-aryl. In one embodiment, one R⁶is methyl and the other R⁶ is benzyl, —C₁-C₆ alkyl-O-phenyl, —C₁-C₆alkyl-O-biphenyl, or —C₁-C₆ alkyl-biphenyl.

The class of compounds according to structure (XXXIV):

wherein each occurrence of R¹⁰ is independently hydrogen, methyl, ethyl,or benzyl.

The class of compounds according to structure (XXXV):

wherein each occurrence of Q² is independently S, O, or N—R⁷ wherein R⁷is hydrogen or C₁-C₆ alkyl; each occurrence of Q¹ is independently S orO; and each occurrence of R⁶ is independently hydrogen, C₁-C₁₂ alkyl,C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or C₁-C₆ alkyl-O-aryl. In one embodiment, one R⁶ ismethyl and the other R⁶ is —C₁-C₆ alkyl-O-phenyl or —C₁-C₆alkyl-O-biphenyl per geminal carbon center.

The class of compounds according to structure (XXXVI):

wherein each occurrence of R¹⁰ is independently hydrogen, methyl, ethyl,or benzyl.

The class of compounds according to structure (XXXVII):

wherein each occurrence of Q² is independently S, O, or N—R⁷ wherein R⁷is hydrogen or C₁-C₆ alkyl; each occurrence of Q¹ is independently S orO; each occurrence of R⁶ is independently hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂haloalkoxy, aryl, —C₁-C₆ alkyl-O—C₁-C₆alkyl, or C₁-C₆ alkyl-O-aryl; and

represents an aryl. In one embodiment, one R⁶ is methyl and the other R⁶is —C₁-C₆ alkyl-O-phenyl or —C₁-C₆ alkyl-O-biphenyl per geminal carboncenter.

The class of compounds according to structure (XXXVIII):

wherein each occurrence of Q² is independently S, O, or N—R⁷ wherein R⁷is hydrogen or C₁-C₆ alkyl; each occurrence of Q¹ is independently S orO; and each occurrence of R⁶ is independently hydrogen, C₁-C₁₂ alkyl,C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl.

The class of compounds according to structure (XXXIX):

wherein each occurrence of Q² is independently S, O, or N—R⁷ wherein R⁷is hydrogen or C₁-C₆ alkyl; each occurrence of Q¹ is independently S orO; and each occurrence of R⁶ is independently hydrogen, C₁-C₁₂ alkyl,C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₁-C₁₂ haloalkoxy, aryl, —C₁-C₆alkyl-O—C₁-C₆ alkyl, or —C₁-C₆ alkyl-O-aryl.

In one embodiment, the copolymer comprises 1 to about 99 percentsubstituted ProDOS/DTS monomer units, specifically about 20 to about 90percent, more specifically about 30 to about 80 percent, and yet morespecifically about 40 to about 70 percent substituted ProDOS/DTS monomerunits present in the copolymer based on the total units of thecopolymer.

As used herein, “alkyl” includes straight chain, branched, and cyclicsaturated aliphatic hydrocarbon groups, having the specified number ofcarbon atoms, generally from 1 to about 20 carbon atoms, specificallyabout 3 to about 15, and more specifically about 5 to about 10 for thestraight chain; and generally from 3 to about 20 carbon atoms,specifically about 4 to about 16, and more specifically about 6 to about12 for the branched and cyclic. Examples of alkyl include, but are notlimited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, 3-methylbutyl,t-butyl, n-pentyl, sec-pentyl, cyclopentyl, cyclohexyl, and octyl.Specific alkyl groups include lower alkyl groups, those alkyl groupshaving from 1 to about 8 carbon atoms, from 1 to about 6 carbon atoms,or from 1 to about 4 carbons atoms.

As used herein “haloalkyl” indicates straight chain, branched, andcyclic alkyl groups having the specified number of carbon atoms,substituted with 1 or more halogen atoms, generally up to the maximumallowable number of halogen atoms (“perhalogenated”, e.g.perfluorinated). Examples of haloalkyl include, but are not limited to,trifluoromethyl, difluoromethyl, 2-fluoroethyl, and penta-fluoroethyl.

As used herein, “alkoxy” includes an alkyl group as defined above withthe indicated number of carbon atoms attached through an oxygen bridge(—O—). Examples of alkoxy include, but are not limited to, methoxy,ethoxy, n-propoxy, i-propoxy, n-butoxy, 2-butoxy, t-butoxy, n-pentoxy,2-pentoxy, 3-pentoxy, isopentoxy, neopentoxy, n-hexoxy, 2-hexoxy,3-hexoxy, and 3-methylpentoxy.

“Haloalkoxy” indicates a haloalkyl group as defined above attachedthrough an oxygen bridge.

As used herein, the term “aryl” indicates aromatic groups containingonly carbon in the aromatic ring or rings. Such aromatic groups may befurther substituted with carbon or non-carbon atoms or groups. Typicalaryl groups contain 1 or 2 separate, fused, or pendant rings and from 6to about 12 ring atoms, without heteroatoms as ring members. Whereindicated aryl groups may be substituted. Such substitution may includefusion to a 5 to 7-membered saturated cyclic group that optionallycontains 1 or 2 heteroatoms independently chosen from N, O, and S, toform, for example, a 3,4-methylenedioxy-phenyl group. Aryl groupsinclude, for example, phenyl, naphthyl, including 1-naphthyl and2-naphthyl, anthracene, pentacene, fluorene, and bi-phenyl.

“Halo” or “halogen” as used herein refers to fluoro, chloro, bromo, oriodo.

Compounds are described using standard nomenclature. For example, anyposition not substituted by any indicated group is understood to haveits valency filled by a bond as indicated, or a hydrogen atom. A dash(“—”) that is not between two letters or symbols is used to indicate apoint of attachment for a substituent. For example, —CHO is attachedthrough carbon of the carbonyl group.

Also contemplated herein are blends comprising two or more substitutedProDOS/DTS polymers. Additionally, blends comprising at least one of theforegoing substituted ProDOS/DTS polymers and an additional polymer arealso contemplated. The additional polymer may be a conductive polymer, anonconductive polymer, a thermoplastic or combinations comprising atleast one of the foregoing.

In one method, a substituted ProDOS/DTS monomer and an optionalco-monomer is chemically oxidized in a liquid to form the substitutedProDOS/DTS polymer. Suitable oxidants include the iron (III) salts oforganic acids, inorganic acids containing organic residues, andinorganic acids, such as FeCl₃, Fe(ClO₄)₃. Oxidants such as H₂O₂,K₂Cr₂O₇, alkali or ammonium persulfates, alkali perborates, potassiumpermanganate, NOBF₄, or copper salts such as copper tetrafluoroboratemay also be used. In addition, bromine, iodine, and oxygen mayadvantageously be used as oxidants. Persulfates and the iron (III) saltsof organic acids and inorganic acids containing organic residues can beused because they are not corrosive. Examples of suitable iron (III)salts of organic acids are the Fe(III) salts of C₁-C₃₀ alkyl sulfonicacids, such as methane or dodecane sulfonic acid; aliphatic C₁-C₂₀carboxylic acids, such as 2-ethylhexylcarboxylic acid; aliphatic C₁-C₂₀perfluorocarboxylic acids, such as trifluoroacetic acid andperfluorooctanoic acid; aliphatic dicarboxylic acids, such as oxalicacid; and aromatic, optionally C₁-C₂₀ alkyl-substituted sulfonic acids,such as benzenesulfonic acid, p-toluene-sulfonic acid and dodecylbenzenesulfonic acid. Mixtures of the aforementioned Fe(III) salts oforganic acids may also be used. Examples of iron (III) salts ofinorganic acids containing organic residues are the iron (III) salts ofsulfuric acid semesters of C₁-C₂₀ alkanols, for example the Fe(III) saltof lauryl sulfate.

Suitable liquids for conducting the oxidative chemical reaction arethose that do not adversely affect the reaction, and specifically areinert. Suitable liquids can further be selected on the basis ofeconomics, environmental factors, and the like, and may be organic,aqueous, or a mixture thereof. Suitable organic liquids may be aliphaticalcohols such as methanol and ethanol; aliphatic ketones such as acetoneand methyl ethyl ketone; aliphatic carboxylic esters such as ethylacetate; aromatic hydrocarbons such as toluene and xylene; aliphatichydrocarbons such as hexane; aliphatic nitriles such as acetonitrile;chlorinated hydrocarbons such as dichloromethane; aliphatic sulfoxidessuch as dimethyl sulfoxide; and the like, as well as mixtures comprisingat least one of the foregoing organic liquids. Specifically aqueousliquids are used, that is, a liquid comprising water or water-miscibleorganic liquids such as lower alcohols, acetonitrile, tetrahydrofuran,dimethylacetamide, dimethylformamide, and the like.

Heat may not be necessary for the formation of the substituted ProDOSpolymer in the chemical oxidation process. However, it can be used tospeed up the conversion to the conjugated polymers. Heat can beadministered to the reaction medium either during its exposure tochemical oxidants or after the exposure. Typical reaction conditionsinclude temperatures of about 0 to about 100° C. The oxidation iscontinued for a period of time until the desired conjugated polymer isprepared. The polymerization time may be a few minutes up to about 48hours, and depends on a number of factors including the size of thereactor utilized, the reaction temperature, the oxidant utilized, andthe like.

In one embodiment, a substituted ProDOS monomer and an optionalco-monomer is converted to a conjugated polymer by a chemical oxidantsuch as FeCl₃ or those previously discussed. When a chemical oxidant isused, the addition of a salt to the reaction solution can be used to getadequate oxidation. Suitable salts for this purpose include organicsoluble salts, inorganic salts, ionic liquids, and polyelectrolytes suchas polystyrene sulfonate, polyacrylic acid sodium salt,poly(meth)acrylic acid sodium salt, etc. Exemplary salts includetetra-alkyl ammonium, ammonium, lithium, or sodium cations withtetrafluoroborate, hexafluorophosphate, perchlorate, halides,toluenesulfonate and other aliphatic sulfonate salts,trifluoromethylsulfonate, bistrifluoromethanesulfonimide, sulfates,carbonates or persulfates.

An alternative method for preparing the substituted ProDOS/DTS polymeris by electrochemical oxidation to convert a substituted ProDOS/DTSmonomer and an optional co-monomer to a conjugated polymer. Conventionalelectrolytic cells can be used for the reaction. In one embodiment, athree-electrode configuration (working electrode, counter electrode, andreference electrode) in operable communication with an electrolyte isused, comprising a working electrode, specifically a button workingelectrode selected from the group consisting of platinum, gold, vitreouscarbon, and indium doped tin oxide working electrodes or non-buttonelectrodes such as the ITO, and platinum flag, a platinum flag counterelectrode, and an Ag/Ag+ non-aqueous reference electrode.

Suitable electrolytes include tetraalkylammonium salts, e.g.,tetraethylammonium, tetrapropyl ammonium, tetrabutylammonium salts, aswell as salts of cations such as lithium trifluoromethansulfonate.Suitable counter ions include but are not limited inorganic ions such asbistrifluoromethylsulfonimide, tosylate, perchlorate, tetrafluoroborate,hexafluorophosphate, and halides such as chloride, bromide, iodide, andorganic anions such as tosylate, triflate, trifluoromethylsulfonimide,or polyanions, e.g., polystyrenesulfonate, the anionic form of acrylicacid. Solvents may be used to prepare an electrolyte solution, forexample water, ethanol, methanol, acetonitrile, propylene carbonate,tetraglyme, methylene chloride, chloroform, and tetrahydrofuran.Specified solvents are water, acetonitrile, and propylene carbonate.

Other suitable electrolytes include ionic liquids such asbutylmethylimidazolium hexafluorophosphate (BMIM PF₆) andbutylmethylimidizolium tetrafluoroborate (BMIM BF₄).

Specified electrolytes include tetrabutylammoniumperchlorate/acetonitrile, tetrabutylammonium tetrafluoroborate,tetrabutylammonium hexafluorophosphate/acetonitrile, lithiumtrifluoromethansulfonate/acetonitrile, and lithiumtriflate/acetonitrile. Exemplary concentrations of the electrolytes areabout 0.05 to about 0.15, specifically about 0.1 M.

A specified working electrode is a vitreous carbon electrode and theelectrolyte is tetrabutylammonium hexafluorophosphate/acetonitrile.Another specified working electrode is a platinum button electrode andthe electrolyte is tetrabutylammonium hexafluorophosphate/acetonitrile.

The substituted ProDOS/DTS polymers disclosed herein provide for atransition from pure blue to colorless.

The electrical conductivity of the films prepared from the polymers canbe readily modified, if necessary, to meet the requirements of a desiredapplication by doping with conventional acidic dopants (p-dopants) orbasic dopants (n-dopants) known in the art. Suitable p-dopants includemineral acids such as HCl, HNO₃, H₂SO₄, H₃PO₄, HBr, and HI; organicsulfonic acids such as dodecyl benzene sulfonic acid, lauryl sulfonicacid, camphor sulfonic acid, organic acid dyes, methane sulfonic acid,and toluene sulfonic acid; polymeric sulfonic acids such as poly(styrenesulfonic acid) and copolymers of styrene sulfonic acids; carboxylicacids such as adipic acid, azelaic acid, and oxalic acid; andpolycarboxylic acids such as poly(acrylic acid), poly(maleic acid),poly(methacrylic acid), and copolymers formed from acrylic acid, maleicacid, or methacrylic acid. Conventional mixed dopants comprising one ormore of the foregoing, such as a mixture of a mineral acid and anorganic acid, can also be used to impart the desired electroactivecharacter to the films. Suitable basic dopants include, but are notlimited to Na, K, Li, and Ca. Other suitable dopants include I₂, PF₆,SbF₆, and FeCl₃. In some instances the oxidant and the dopant may be thesame.

Admixtures of the polymer with other electroactive materials such aslaser dyes, other electroactive polymers, hole transport or electrontransport materials, including electroactive organometallic compounds,are also contemplated herein. Such materials can be added to the polymerbefore or after formation of the solution or dispersion. Additives suchas ethylene glycol, diethylene glycol, mannitol, propylene 1,3-glycol,butane 1,4-glycol, N-methylpyrrolidone, sorbitol, glycerol, propylenecarbonate, and other appropriate high boiling organics may be added todispersions of the polymeric compositions to improve conductivity.

Additional additives may also be used, and include conductive fillerssuch as particulate copper, silver, nickel, aluminum, carbon black(carbon nanotubes, buckminister fullerene), and the like; non-conductivefillers such as talc, mica, wollastonite, silica, clay, dyes, pigments(zeolites), and the like, to promote specific properties such asincreased modulus, surface hardness, surface color and the like;antioxidants; UV stabilizers; viscosity modifiers; and surfactants suchas acetylenic diols, surfactants typically being added to controlstability, surface tension, and surface wettability.

The substituted ProDOS/DTS polymers are especially useful as chargetransport or semiconductor materials

The substituted ProDOS/DTS polymers disclosed herein can be processed byconventional methods to provide uniform, thin films that possess utilityin numerous applications. Films and materials comprising theabove-described conjugated polymers can be utilized in a variety ofapplications, including antistatic coatings, electrically conductivecoatings, electrochromics, photovoltaic devices, light emitting diodesfor display applications, hole injection layers for light emittingdiodes, near infrared light emitting diodes, transparent conductivecoating for indium doped tin oxide replacement, flat panel displays,flexible displays, photoimageable circuits, printable circuits, thinfilm transistor devices, batteries, electrical switches, capacitorcoatings, corrosion resistant coatings, electromagnetic shielding,sensors, biosensors, dimmable mirrors, type III supercapacitors, LEDlighting, and the like, and specifically electrochromic windows,electrochromic films for reflective devices, and electrochromicdisplays. The electrical conductivity of the polymers can be readilymodified, if necessary, to meet the requirements of any of thepreviously mentioned applications by doping the polymers withconventional dopants such as anions (for p-doped polymers) and cationdopants (for n-doped polymers) known in the art.

The substituted ProDOS/DTS polymers find particular application in theelectrochromic devices with enhanced photopic contrast.

The following illustrative examples are provided to further describe howto make and use the polymers and are not intended to limit the scope ofthe claimed invention.

EXAMPLES Example 1 Preparation ofmeso-2,2,6,6-Tetramethyl-3,5-heptanediol (TMHDio1) (3)

5-Hydroxy-2,2,6,6,-tetramethyheptan-3-one (HTMH-One) (2): To a solutionof pinacolone (10 g, 100 mmol, 1), in anhydrous THF (500 mL), at −78° C.a 2.0 M solution of lithium diisopropylamide (LDA) in hexane (60 mL, 120mmol) over a period of 30 min. The reaction was stirred at −78° C. foranother 30 min. To the resulting white suspension pivalaldehyde (10.9mL, 100 mmol) was added drop-wise via syringe and the reaction continuedfor another 12 hrs at room temperature. The reaction was quenched byadding 10 mL of water. Approximately 80% THF was removed and the mixturewas then poured into saturated aqueous solution of NH₄Cl. The aqueouslayer was extracted twice with diethyl ether (200 mL) and the organiclayer was washed with plenty of water. The organic layer was then driedover MgSO₄ and concentrated to give a crude yellow solid of β-hydroxyketone (17.2 g, 95%, (2)). The crude product was recrystallized fromhexane to give pure white solid with a yield of 81%.

Meso-2,2,6,6-Tetramethyl-3,5-heptanediol (TMHDio1) (3): To a solution ofβ-hydroxy ketone (10 g, 53 mmol, (2)) in THF (250 mL) was added 1 MDiisobutylaluminium hydride (DIBAL-H) in hexane, (118 mL, 118 mmol) at−78° C., and the solution was stirred for 2 hrs at this temperature. Thereaction mixture was allowed to warm to room temperature and continuedfor another 8 hrs at room temperature. After 8 hrs the reaction mixturewas quenched with 2 N aqueous HCl solution. The mixture was thenextracted twice with ether (200 mL), and the combined organic layer waswashed with saturated aqueous NaHCO₃ solution and with brine. Dryingwith anhydrous MgSO₄ and concentration gave the TMHDiol (9 g, 90% yield,(3)) as a white solid.

Example 2 Preparation of 2,2-dihexyl Propane-1,3-diol (6)

Synthesis of 2,2-Dihexylmalonic Acid Diethyl Ester (5): In a 500 mLflame dried three-neck round bottom flask equipped with an argon inletand condenser were combined 200 mL of dry THF, hexyl bromide (0.00 g,1.5 mole), and 3.5 mol of NaH. The flask was cooled to 0° C., and 1.15mol of freshly distilled diethylmalonate (4) was added dropwise viasyringe. After the addition of malonate, the mixture was refluxed for 12h. The flask was then cooled at 0° C. and the remaining sodium hydridewas quenched by adding water dropwise. The mixture was then poured intobrine solution (2 L) and extracted two times with ether. The ether layerwas finally washed with brine and then with water. The organic phase wasdried over MgSO₄, and evaporated to give a light yellow liquid. Thecrude product was further purified by vacuum distillation to provide2,2-dihexylmalonic acid diethyl ester (0.85 g, 70%, (5)) as a colorlessoil.

Synthesis of 2,2-Dihexyl Propane-1,3-diol (6): A suspension of lithiumaluminum hydride (LAH) (2 g, 52.6 mmol) in dry THF (20 mL) was stirredat room temperature, and a THF solution of substituted malonic aciddiethyl ester (26.3 mmol, (5)) was added dropwise. The reaction wasallowed to reflux for 3 h and was quenched by the addition of coldwater. The compound was extracted in ethyl acetate. The organic layerwas washed with water, dried over Na2SO4, and evaporated to produce theproduct (6) as either a sticky liquid or a low-melting solid.

Example 3 Preparation of (3R,5S)-2,6-dimethylheptane-3,5-diol(DMH-Diol)

5-hydroxy-2,6-dimethylheptan-3-one (HDMH-One): To a solution of3-methylbutan-2-one (10 g, 116 mmol (7)), in anhydrous THF (500 mL), at−78° C. was added a 2.0 M solution of LDA in hexane (70 mL, 140 mmol)over a period of 30 min. The reaction was stirred at −78° C. for another30 min. To the resulting white suspension isobutyraldehyde (8.4 mL, 116mmol) was added drop-wise via syringe and the reaction continued foranother 12 hrs at room temperature. The reaction was quenched by adding10 mL of water. Approximately 80% THF was removed and the mixture wasthen poured into saturated aqueous solution of NH₄Cl. The aqueous layerwas extracted twice with diethyl ether (200 mL) and the organic layerwas washed with plenty of water. The organic layer was then dried overMgSO₄ and concentrated to give a crude white oil of (3-hydroxy ketone(16.5 g, 90%). The crude product was recrystallized from petroleum etherto give pure white solid (8) with a yield of 76%.

(3R,5S)-2,6-dimethylheptane-3,5-diol (DMH-Diol) (9): To a solution of(3-hydroxy ketone (10 g, 63 mmol, (8)) in THF (250 mL) was added 1 MDIBAL-H in hexane, (126 mL, 126 mmol) at −78° C., and the solution wasstirred for 2 hrs at this temperature. The reaction mixture was allowedto warm to room temperature and continued for another 8 hrs at roomtemperature. After 8 hrs the reaction mixture was quenched with 2 Naqueous HCl solution. The mixture was then extracted twice with ether(200 mL), and the combined organic layer was washed with saturatedaqueous NaHCO₃ solution and with brine. Drying with anhydrous MgSO₄ andconcentration gave the crude DMH-Diol (8.5 g, 84% yield) as a whitesolid. The crude diol was further purified by column chromatographyusing petroleum ether and ethyl acetate mixture (80:20) to give purifiedproduct (9) with a yield of 72%.

Example 4 Preparation of pentadecane-7,9-diol (10)

A solution of 1M DIBAL-H in toluene (125.0 mL, 125 mmol) was slowlyadded over a period of 10 mins, to a solution of diethylmalonate (10.0mL, 62.5 mmol, (4)) in Et₂O (13.6 mL) at −78° C. under N₂. The internaltemperature was maintained −78° C. The mixture was stirred for 1 h at−78° C. A solution of hexylmagnesium bromide in Et₂O (65.0 mL, 130 mmol)was added at −78° C. The reaction mixture was then warmed to roomtemperature and stirred for 6 h. The mixture was quenched with saturatedNH₄Cl solution at 0° C. A saturated solution of Rochelle's salt wasadded at room temperature and the two-phase mixture was stirred forapproximately 8 h. The aqueous layer was extracted with ethyl acetate.The combined organic layers were dried over Na₂SO₄. The solvent wasremoved in vacuum, and the resulting material was purified via columnchromatography (30% Ethyacetate-70% hexanes) to provide the desiredproduct (6.4 g, 42%, (10)).

Example 5 Preparation of 3,4-dimethoxyselenophene (DMOS) (12)

SeCl₂ was prepared by adding SO₂Cl₂ (2.0 g, 14.8 mmol) to seleniumpowder (1.18 g, 14.8 mmol) over a period of 5 min at 10-20° C. After 30min, 10 mL hexane was added to it and the resulting reaction mixture wasstirred for 4 h at room temperature. A clear brown solution of SeCl₂ wasformed.

To a well stirred solution of 2,3-dimethoxy-1,3-butadiene (1.47 g, 12.9mmol, (11)) and CH₃COONa (2.64 g, 32.25 mmol) in dry hexane (80 mL) at−78° C. (dry ice/acetone bath), under an inert atmosphere, was added asolution of freshly prepared SeCl₂ in hexane over a period of 15 min.The resulting yellowish solution was further stirred for 1 h at −78° C.and then removed from the cooling bath and the reaction mixture wasbrought to room temperature over a period of 2 h and further stirred for5 h. The reaction mixture was filtered through neutral alumina andwashed with hexane. The residue was concentrated to give brown yellowoil. The crude product was purified by flash column chromatography onTLC grade silica gel (Hexane:Ethyl acetate—95:5) to provide DMOS (0.85g, 35%, (12)) as a white crystalline solid. mp. 43-45° C.

Example 6 Preparation of2,2-Dihexyl(3,4-propylenedioxyselenophene)(ProDOS-Hex₂) (13)

3,4-Dimethoxyselonophene (DMOS) (0.5 g, 2.60 mmol (12)), 2,2-dihexylpropane-1,3-diol (0.54 g, 5.20 mmol (6)), dodecylbenzene sulfonic acid(DBSA) (0.17 g, 0.52 mmol) and 100 mL of dry toluene were combined in a3-neck round bottom flask equipped with a Soxhlet extractor with type 4molecular sieves in the thimble. The solution was heated to reflux andallowed to reflux for 6 h. The reaction mixture was cooled, washed withdilute NaHCO3 solution and finally with water. Solid NaCl is used as anemulsion breaker. The toluene was removed under vacuum, and the crudeproduct was purified by column chromatography on silica gel with 4:1hexanes/ethylacetate as the eluent to yield ProDOS-Hex₂ (13) as a whitesolid (0.39 g, 65%). ProDOS-Hex₂ was characterized by using ¹H-NMR,¹³C-NMR, ⁷⁷Se-NMR, GC-MS and GPC.

¹H-NMR (500 MHz, CDCl₃) δ 6.97 (s, 2H), 3.72 (s, 4H), 1.02 (s, 6H); ¹³CNMR: δ 151.44, 108.37, 80.05, 39.18, 21.98. ⁷⁷Se NMR (400 MHz, CDCl₃)δ=394.9 ppm.

Example 7 Preparation of 2,2-Dimethyl(3,4-propylenedioxyselenophene)(ProDOS-Me₂) (15)

3,4-Dimethoxyselonophene (DMOS) (0.5 g, 2.60 mmol (12)), neopentylglycol (0.54 g, 5.20 mmol (14)), dodecylbenzene sulfonic acid (DBSA)(0.17 g, 0.52 mmol) and 100 mL of dry toluene were combined in a 3-neckround bottom flask equipped with a Soxhlet extractor with type 4 Amolecular sieves in the thimble the synthetic scheme is shown in thefollowing scheme. The solution was heated to reflux and allowed toreflux for 12 hrs. The reaction mixture was cooled, washed with diluteNaHCO₃ solution and finally with water. Solid NaCl is used as anemulsion breaker. The toluene was removed under vacuum, and the crudeproduct was purified by column chromatography on silica gel with 4:1hexanes/ethylacetate as the eluent to yield Pro-DOS-Me₂ (15) as a whitesolid (0.39 g, 52%). ProDOS-Me₂ was characterized by using ¹H-NMR,¹³C-NMR, ⁷⁷Se-NMR, GC-MS and GPC.

¹H-NMR (500 MHz, CDCl₃): δ 6.97 (s, 2H), 3.72 (s, 4H), 1.02 (s, 6H); ¹³CNMR: δ 151.44, 108.37, 80.05, 39.18, 21.98. ⁷⁷Se NMR (400 MHz, CDCl₃)δ=394.9 ppm.

Example 8 Preparation of 3,4-dimethyl substituted3,4-propylenedioxyselenophene (ProDOS-3,4-Me₂) (17)

A transetherfication of 3,4-Dimethoxyselonophene (DMOS) (0.5 g, 2.60mmol (12) with 2,4-pentanediol (16) in the presence of a catalyticamount of p-toluenesulfonic acid (p-TSA) or DBSA in toluene or xylenewill produce ProDOS-3,4-Me₂ (17).

Example 9 Preparation of 3,4-ditert-butyl substituted3,4-propylenedioxyselenophene (ProDOS-3,44-butyl₂) (18)

A transetherfication of 3,4-Dimethoxyselonophene (DMOS) (0.5 g, 2.60mmol (12) with diol (3) in the presence of a catalytic amount ofp-toluenesulfonic acid (p-TSA) or DBSA in toluene or xylene will produceProDOS-3,44-butyl₂) (18).

Example 10 Preparation of 3,4-diisopropyl substituted3,4-propylenedioxyselenophene (ProDOS-3,4-isopropyl₂) (19)

A transetherfication of 3,4-Dimethoxyselonophene (DMOS) (0.5 g, 2.60mmol (12) with diol (9) in the presence of a catalytic amount ofp-toluenesulfonic acid (p-TSA) or DBSA in toluene or xylene will produceProDOS-3,4-isopropyl₂) (19).

Example 11 Preparation of 3,4-dihexyl substituted3,4-propylenedioxyselenophene (ProDOS-3,4-hexyl₂) (20)

A transetherfication of 3,4-Dimethoxyselonophene (DMOS) (0.5 g, 2.60mmol (12) with diol (10) in the presence of a catalytic amount ofp-toluenesulfonic acid (p-TSA) or DBSA in toluene or xylene will produceProDOS-3,4-hexyl₂ (20).

Example 12 Polymerization of DibromoProDOS-Hex₂

Chemical polymerization of DibromoProDOS-Hex₂ (21) was performed usingFeCl₃ to form polyProDOS-Hex₂. PolyProDOS-Hex₂ is soluble in commonorganic solvents with a number average molecular weight of about 5800g/mole. The soluble polymer obtained from ProDOS-Hex₂ was characterizedby using ¹H-NMR, ¹³C-NMR, ⁷⁷Se-NMR, GC-MS and GPC.

Example 13

In-situ spectroelectrochemistry of PProDOS-Me₂ deposited ontoITO-coated-glass in 0.1 M TBAPF₆/ACN is illustrated in FIG. 1. Appliedpotential a) 0.6, b) 0.4 c) 0.2, d) 0.0, e) −0.1, f) −0.2, g) −0.3, h)−0.4, i) −0.5, j) −0.6 V vs non-aqueous Ag—Ag+ reference electrode(0.445 V vs NHE).

Example 14

In-situ spectroelectrochemistry of PProDOS-Hexyl₂ deposited ontoITO-coated-glass in 0.1 M TBAPF₆/ACN is illustrated in FIG. 2. Appliedpotential of a) 0.6, b) 0.4 c) −0.4, d) −0.6 V vs non-aqueous Ag—Ag+reference electrode (0.445 V vs NHE).

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. The terms “comprising”, “having”, “including”, and “containing”are to be construed as open-ended terms (i.e., meaning “including, butnot limited to”) unless otherwise noted. “Or” means and/or. Recitationof ranges of values herein are merely intended to serve as a shorthandmethod of referring individually to each separate value falling withinthe range, unless otherwise indicated herein, and each separate value isincorporated into the specification as if it were individually recitedherein. All ranges disclosed herein are inclusive and combinable.

The essential characteristics of the present invention are describedcompletely in the foregoing disclosure. One skilled in the art canunderstand the invention and make various modifications withoutdeparting from the basic spirit of the invention, and without deviatingfrom the scope and equivalents of the claims, which follow. Moreover,any combination of the above-described elements in all possiblevariations thereof is encompassed by the invention unless otherwiseindicated herein or otherwise clearly contradicted by context.

What is claimed is:
 1. A compound, comprising: a monomer according toany one of structure (I), (Ia), (II), and (IIa):

wherein each instance of Q is O or S; X is chloro, bromo, or iodo; eachof R^(1a), R^(1b), R^(2a), R^(2b), R³, and R⁴ independently is hydrogen;C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl, C₁-C₂₀ alkoxy, C₁-C₂₀ haloalkoxy,aryloxy, —C₁-C₁₀ alkyl-O—C₁-C₁₀alkyl, —C₁-C₁₀alkyl-O-aryl,—C₁-C₁₀alkyl-aryl; or hydroxyl; with the proviso that at least one ofR^(1a), R^(1b),R^(2a)R^(2b), R³, and R⁴is not hydrogen, and when R^(1a),R^(1b), R^(2a), and R^(2b) are all hydrogen, then at least one of R³ andR⁴ is other than hydrogen, C₁-C₂₀ alkyl, or —C₁-C₁₀ alkyl-aryl; whereinthe C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl, C₁-C₂₀ alkoxy, C₁-C₂₀haloalkoxy, aryloxy, —C₁-C₁₀ alkyl-O—C₁-C₁₀ alkyl,—C₁-C₁₀ alkyl-O-aryl,—C₁-C₁₀ alkyl-aryl group each may be optionally substituted with one ormore of C₁-C₂₀ alkyl; aryl; halogen; hydroxyl; —N—(R⁷)₂ wherein each R⁷is independently hydrogen or C₁-C₆ alkyl; cyano; nitro; —COOH;—S(═O)C₀-C₁₀ alkyl; or —S(═O)₂C₀-C₁₀ alkyl.
 2. The compound of claim 1,wherein both Q groups are O.
 3. The compound of claim 1, wherein both Qgroups are S.
 4. The compound of claim 1, wherein each of R^(1a),R^(1b), R^(2a) and R^(2b) independently is hydrogen; optionallysubstituted C₁-C₁₀ alkyl, C₁-C₁₀ haloalkyl, aryl, C₁-C₁₀ alkoxy, C₁-C₁₀haloalkoxy, aryloxy, —C₁C₅ alkyl-O—C₁C₅ alkyl, —C₁-C₅ alkyl-O-aryl,—C₁-C₅ alkyl-aryl; or hydroxyl; and R³ and R⁴ are both hydrogen, withthe proviso that at least one of R^(1a), R^(1b), R^(2a), and R^(2b) isnot hydrogen.
 5. The compound of claim 1, wherein each of R^(1a),R^(1b),R^(2a) and R^(2b) independently is hydrogen; optionally substitutedC₁-C₅ alkyl, C₁-C₅ haloalkyl, aryl, C₁-C₅ alkoxy, C₁-C₅ haloalkoxy,aryloxy, —C₁-C₃ alkyl-O—C₁-C₃ alkyl, —C₁-C₃ alkyl-O-aryl, —C₁-C₃alkyl-aryl; or hydroxyl; and R³ and R⁴ are both hydrogen, with theproviso that at least one of R^(1a), R^(1b), R^(2a), and R^(2b) is nothydrogen.
 6. The compound of claim 1, wherein each of R^(1a), R^(1b),R^(2a) and R^(2b) independently is hydrogen; or optionally substitutedC₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl, —C₁-C₁₀ alkyl-aryl; and R³ and R⁴are both hydrogen, with the proviso that at least one of R^(1a), R^(1b),R^(2a), and R^(2b) is not hydrogen.
 7. The compound of claim 1, whereineach of R^(1a), R^(1b), R^(2a) and R^(2b) independently is hydrogen; oroptionally substituted C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, aryl, —C₁-C₁₀alkyl-aryl; and R³ and R⁴ are both hydrogen, with the proviso that atleast two of R^(1a), R^(1b), R^(2a) and R^(2b) are not hydrogen.
 8. Thecompound of claim 1, wherein at least two of and R^(1a), R^(1b), R^(2a),and R^(2b) are not hydrogen while the remaining two are hydrogen.
 9. Thecompound of claim 1, wherein R^(1a), R^(1b), R^(2a), and R^(2b) are allhydrogen; R³ and R⁴ are each independently optionally substituted C₃-C₂₀alkyl, C₃-C₂₀ haloalkyl, aryl, C₃-C₂₀ alkoxy, C₃-C₂₀ haloalkoxy,aryloxy, —C₁-C₁₀ alkyl-O—C₁-C₁₀ alkyl, —C₁-C₁₀ alkyl-O-aryl, —C₃-C₁₀alkyl-aryl.
 10. An article comprising the compound of any one of claims1-9.